CN115448382B - High-nickel ternary precursor and preparation method and application thereof - Google Patents
High-nickel ternary precursor and preparation method and application thereof Download PDFInfo
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- CN115448382B CN115448382B CN202211110777.4A CN202211110777A CN115448382B CN 115448382 B CN115448382 B CN 115448382B CN 202211110777 A CN202211110777 A CN 202211110777A CN 115448382 B CN115448382 B CN 115448382B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002243 precursor Substances 0.000 title claims abstract description 74
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 238000000975 co-precipitation Methods 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000012716 precipitator Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 110
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 38
- 239000011164 primary particle Substances 0.000 abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 19
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 238000010900 secondary nucleation Methods 0.000 abstract description 4
- 230000008092 positive effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 39
- 239000002245 particle Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 21
- 239000008139 complexing agent Substances 0.000 description 20
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 11
- 229910001429 cobalt ion Inorganic materials 0.000 description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 229910001437 manganese ion Inorganic materials 0.000 description 11
- 229910001453 nickel ion Inorganic materials 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- FWHZQBMZKQZFJG-UHFFFAOYSA-N manganese hydrochloride Chemical compound Cl.[Mn] FWHZQBMZKQZFJG-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- XATZQMXOIQGKKV-UHFFFAOYSA-N nickel;hydrochloride Chemical compound Cl.[Ni] XATZQMXOIQGKKV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a high-nickel ternary precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding metal salt, ammonia water and a precipitator into a base solution containing the precipitator and the ammonia water and having the oxygen content lower than 1% respectively for coprecipitation reaction to obtain the high nickel ternary precursor; the coprecipitation reaction is as follows: firstly, introducing protective gas to react, and then introducing oxygen-containing gas to react, wherein the temperature of the coprecipitation reaction is 25-40 ℃, and the concentration of ammonia water is 0.5-2.5 g/L. The preparation method of the invention reduces the agglomeration problem in the early stage of the reaction by using the anaerobic base solution and introducing nitrogen to form nuclei in the early stage of the reaction; the whole preparation process is carried out under extremely low ammonia concentration, so that primary particles can be refined; the invention adopts lower reaction temperature, which has positive effect on primary particle refinement on one hand and can avoid secondary nucleation in low ammonia environment on the other hand.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a high-nickel ternary precursor, and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the fields of electric vehicles, electric tools, 3C and the like by virtue of the advantages of stable voltage, high capacity, high energy density, less self discharge, stable circulation, low consumption, environmental friendliness and the like, and along with the development of technology, the energy density and the safety requirements of the battery are higher and higher, the ternary system material has high reversible specific capacity, the requirements of increasingly miniaturization and multifunctionality of electronic products can be better met, and the physical and chemical indexes such as morphology, granularity, specific surface area, tap density and the like of the ternary precursor determine the performance of the ternary positive electrode material to a great extent.
The high-nickel monocrystal ternary anode material has the advantages of high specific capacity, small pollution, moderate price, good matching with electrolyte and the like, becomes a focus of attention of the anode material, is considered as an anode material of a lithium ion battery with very good development prospect, and has very wide market in the field of power batteries. Compared with the high-nickel polycrystalline ternary positive electrode material, the high-nickel monocrystal ternary positive electrode material has less grain boundary, low internal resistance and better cycle performance. In addition, the mechanical strength of the high-nickel single crystal ternary positive electrode material is higher than that of the high-nickel polycrystalline ternary positive electrode material, and the high-nickel single crystal ternary positive electrode material has higher compaction density.
In actual production, the coprecipitation method is adopted to prepare a ternary precursor, particles of the ternary precursor are easy to agglomerate, twin balls or agglomerates are generated, and sphericity is poor. The agglomeration phenomenon of the ternary precursor particles has adverse effects on the physical and chemical indexes and the electrical properties of subsequent products. In order to improve the energy density and charge-discharge performance of the ternary lithium ion battery, the ternary precursor material is required to have both a high Tap Density (TD) and a high specific surface area (BET). While refining primary particles is an effective way for improving tap density and specific surface area at the same time, the existing preparation method is to refine the primary particles, and generally adopts higher pH value or lower ammonia concentration to refine the primary particles, and the method easily causes secondary nucleation of the precursor in the subsequent reaction process, damages the particle size distribution of the primary particles and forms more serious agglomeration, so that the prepared positive electrode material has lower energy density and poorer charge and discharge performance. In order to solve the above problems in the prior art in refining primary particles, it is necessary to develop a method for preparing a high-dispersion high-nickel ternary precursor.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide a preparation method of a high-nickel ternary precursor, wherein the high-nickel ternary precursor prepared by the preparation method has high dispersibility.
The second purpose of the invention is to provide a high nickel ternary precursor.
The invention further aims to provide application of the high-nickel ternary precursor in the field of lithium ion batteries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of a high-nickel ternary precursor, which comprises the following steps:
adding metal salt, ammonia water and a precipitator into a base solution containing the precipitator and the ammonia water and having the oxygen content lower than 1% respectively for coprecipitation reaction to obtain the high nickel ternary precursor;
the coprecipitation reaction is as follows: firstly, introducing protective gas to react, then introducing oxygen-containing gas to react,
the temperature of the coprecipitation reaction is 25-40 ℃, and the concentration of ammonia water is 0.5-2.5 g/L.
According to the invention, the base solution with the oxygen content lower than 1% is used, and nitrogen is introduced, so that the sphericity of the initial stage of the reaction is improved; then oxygen-containing gas is introduced to oxidize through air, so that the reaction rate is improved, and primary particles are further refined; the whole preparation process can refine primary particles through the combined action of extremely low temperature and ammonia concentration, and can avoid secondary nucleation and agglomeration of the primary particles to optimize sphericity.
Preferably, the pH of the base liquid is 10.5 to 11.0.
Preferably, the concentration of ammonia water in the base solution is 0.5-2.5 g/L.
Preferably, the temperature in the base liquid is 25-40 ℃.
Preferably, the preparation method of the base solution comprises the following steps: and (3) introducing protective gas into the base solution containing the precipitator and the ammonia water to ensure that the oxygen content in the base solution is lower than 1%.
Preferably, in the preparation method of the base solution, the time required for introducing the protective gas is 4-6 hours. The time and amount of the shielding gas introduced into the base liquid are determined according to the oxygen content in the base liquid, and when the oxygen content in the base liquid is lower than 1%, the introduction of the shielding gas can be stopped.
Preferably, the metal salt is a metal salt solution.
Preferably, the adding flow rate of the metal salt solution is 100-800L/h.
Preferably, the total concentration of metal ions in the metal salt solution is 115-125 g/L.
Preferably, the metal salt solution is a soluble salt solution of nickel cobalt manganese.
Preferably, in the metal salt solution, the molar ratio of nickel ions, cobalt ions and manganese ions is x: y: z, wherein x+y+z=100, 90+.x <98,0< y <5, z > 0.
Preferably, the soluble salt solution of nickel cobalt manganese comprises at least one of sulfate solution, nitrate solution and hydrochloride solution.
Preferably, the sulfate solution includes at least one of nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution.
Preferably, the nitrate solution comprises at least one of a nickel nitrate solution, a cobalt nitrate solution, and a manganese nitrate solution.
Preferably, the hydrochloride solution comprises at least one of nickel hydrochloride solution, cobalt hydrochloride solution and manganese hydrochloride solution.
Preferably, the adding flow rate of the precipitant is 50-400L/h.
Preferably, the concentration of the precipitant is 6-10 mol/L; further preferably, the concentration of the precipitant is 7 to 9mol/L; still further preferably, the concentration of the precipitant is 8mol/L.
Preferably, the precipitating agent comprises an alkaline solution.
Preferably, the alkali liquor is at least one of sodium hydroxide and potassium hydroxide.
Preferably, the lye is an industrial lye.
Preferably, the adding flow rate of the ammonia water is 1-100L/h.
Preferably, the concentration of the ammonia water is 0.4-0.8 mol/L; further preferably, the concentration of the ammonia water is 0.5 to 0.7mol/L; still further preferably, the concentration of the aqueous ammonia is 0.6mol/L.
Preferably, the time required for the step of adding the metal salt, the ammonia water and the precipitant is 60 to 70 hours.
Preferably, the flow ratio of the shielding gas to the metal salt solution is (2-3): 1.
preferably, the flow rate ratio of the oxygen-containing gas to the metal salt solution is (0.1 to 0.5): 1.
preferably, in the coprecipitation reaction, the time required for introducing the protective gas is 4-6 hours.
Preferably, the shielding gas used in the present invention includes at least one of nitrogen, argon, helium; further preferably, the shielding gas is nitrogen.
Preferably, in the coprecipitation reaction, the time required for introducing oxygen-containing gas is 54-66 hours.
Preferably, the oxygen-containing gas comprises at least one of air and oxygen; further preferably, the oxygen-containing gas is air.
Preferably, the pH of the coprecipitation reaction is 9.5 to 10.
Preferably, the time of the coprecipitation reaction is 60 to 70 hours.
Preferably, the preparation process is carried out in a reaction vessel with a stirrer.
Preferably, the positions of the liquid inlets of the metal salt solution, the ammonia water and the precipitant are the same as the positions of the gas inlets of the nitrogen, and the gas outlet of the nitrogen is positioned above the stirrer in the reaction vessel.
Preferably, the oxygen content in the reaction vessel is < 1%.
Preferably, the stirring speed of the coprecipitation reaction is 300-500 r/min; further preferably, the stirring speed of the coprecipitation reaction is 350 to 450r/min.
Preferably, the preparation method further comprises the steps of aging, washing and drying; the aging, washing and drying steps are located after the coprecipitation reaction step.
Preferably, the base solution also contains an antioxidant, and the antioxidant is at least one of ascorbic acid and hydrazine hydrate. The antioxidant is added into the reaction base solution, so that the surface viscosity of the small particles can be further reduced, the early agglomeration of the small particles is reduced, and the sphericity is optimized.
Preferably, the preparation method further comprises the step of monitoring particle size; the step of monitoring particle size is located during the step of co-precipitation. The particle size is required to be continuously monitored in the coprecipitation reaction process, a high-efficiency thickener is used in the reaction process before the particle size does not meet the requirement, all particles are collected and returned to the reaction kettle at any time to continuously react and grow, and when the particle size D50 reaches 2.0-4.0 mu m, feeding is stopped until the material is completely reacted, so that the superfine high-nickel ternary precursor with the nickel content of 90-98mol% is obtained.
In a second aspect, the invention provides a high nickel ternary precursor prepared by the method provided in the first aspect.
Preferably, in the precursor, the molar ratio of nickel element, cobalt element and manganese element is x: y: z, wherein x+y+z=100, 90+.x <98,0< y <5, z > 0.
Preferably, the nickel content in the precursor is 90-98%.
Preferably, D of the precursor 50 Is 2-4 mu m.
Preferably, the specific surface area of the precursor is 45-70m 2 /g。
The third aspect of the invention provides application of the high-nickel ternary precursor in the field of lithium ion batteries.
The beneficial effects of the invention are as follows: according to the preparation method, the base solution with the oxygen content lower than 1% is used in the early stage of the reaction, and nitrogen is introduced to form nuclei, so that the agglomeration problem in the early stage of the reaction can be reduced to a certain extent; the whole preparation process can refine primary particles under extremely low ammonia concentration, and the existing conventional process adopts low ammonia concentration reaction to secondarily nucleate in the later period and seriously influence the particle distribution and sphericity; in addition, the reaction rate is improved on the one hand, primary particles are further refined on the other hand by air quantitative oxidation at the later stage of the preparation process, and the specific surface area and tap density of the prepared high-nickel ternary precursor are further improved.
The nickel content of the high-nickel ternary precursor reaches 90-98%, the high-nickel ternary precursor has primary particles with high dispersibility, no agglomeration and ultrafine morphology, and simultaneously has high specific surface area and tap density,wherein the specific surface area can reach 45-70m 2 And/g, the ternary precursor is applied to a lithium ion battery, so that the electrical performance of the battery can be remarkably improved.
Drawings
Fig. 1 is an SEM image of the high nickel ternary precursor prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the high nickel ternary precursor prepared in example 2 of the present invention.
Fig. 3 is an SEM image of the high nickel ternary precursor prepared in comparative example 1 of the present invention.
Fig. 4 is an SEM image of the high nickel ternary precursor prepared in comparative example 2 of the present invention.
Fig. 5 is an SEM image of the high nickel ternary precursor prepared in comparative example 3 of the present invention.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the drawings and examples, but the practice and protection of the present invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1:
the high-nickel ternary precursor in the example is prepared by adopting the following preparation method, and specifically comprises the following steps:
(1) Preparing sulfate solution A containing nickel ions, cobalt ions and manganese ions and having the total ion concentration of 120g/L, wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 94:2:4, industrial liquid alkali with the concentration of 8mol/L is used as precipitant solution B, and ammonia water with the concentration of 0.6mol/L is used as complexing agent solution C;
(2) 6000L of distilled water is added into a reaction kettle, 8mol/L of precipitator solution B and 0.6mol/L of complexing agent solution C are added, a base solution D with pH of 11.00 and ammonia concentration of 1.5g/L is obtained, the temperature of the base solution D is 35 ℃, and nitrogen is introduced into the base solution D for about 5 hours, so that the dissolved oxygen content of the base solution D is lower than 1mg/L. And adding the sulfate solution A, the precipitator solution B and the complexing agent solution C into the base solution D according to the flow rates of 600L/h, 240L/h and 8L/h respectively to carry out coprecipitation reaction, wherein the ammonia concentration of a reaction system in the coprecipitation reaction process is 1.5g/L, the reaction pH is 9.60, the temperature is 35 ℃, and the stirring rotation speed is 400rpm. After the coprecipitation reaction starts, continuously introducing nitrogen for 5 hours, wherein the flow rate of the nitrogen is 1000L/h, and then, continuously introducing air for reaction for about 60 hours, wherein the flow rate ratio of the air flow to the sulfate solution A is 0.8; stopping introducing the sulfate solution A, the precipitator solution B and the complexing agent solution C until the reaction is completed when the precursor particles grow to the target particle diameter of 3 mu m, ending the reaction to obtain a spherical high-nickel ternary precursor, and performing treatments such as centrifugation, washing, drying and removing magnetic foreign matters to obtain a spherical high-nickel ternary precursor finished product material.
Example 2:
the high-nickel ternary precursor in the example is prepared by adopting the following preparation method, and specifically comprises the following steps:
(1) Preparing sulfate solution A containing nickel ions, cobalt ions and manganese ions and having the total ion concentration of 120g/L, wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 96:1:3, industrial liquid alkali with the concentration of 8mol/L is used as precipitant solution B, and ammonia water with the concentration of 0.6mol/L is used as complexing agent solution C;
(2) 6000L of distilled water is added into a reaction kettle, 8mol/L of precipitator solution B and 0.6mol/L of complexing agent solution C are added, a base solution D with pH of 11.00 and ammonia concentration of 1.0g/L is obtained, the temperature of the base solution D is 40 ℃, and nitrogen is introduced into the base solution D for about 5 hours, so that the dissolved oxygen content of the base solution D is lower than 1mg/L. And adding the sulfate solution A, the precipitator solution B and the complexing agent solution C into the base solution D according to the flow rates of 600L/h, 240L/h and 8L/h respectively to carry out coprecipitation reaction, wherein the ammonia concentration of a reaction system in the coprecipitation reaction process is 1.5g/L, the reaction pH is 9.60, the temperature is 40 ℃, and the stirring rotation speed is 400rpm. After the coprecipitation reaction starts, nitrogen is continuously introduced for 5 hours, the flow rate of the nitrogen is 1000L/h, air is introduced again for continuous reaction for about 60 hours, the flow rate ratio of the air flow rate to the sulfate solution A is 0.6, the introduction of the sulfate solution A, the precipitator solution B and the complexing agent solution C is stopped when the precursor particles grow to the target particle size of 3 mu m until the reaction is completed, the reaction is ended, the spherical high-nickel ternary precursor is obtained, and the spherical high-nickel ternary precursor finished product material is obtained after the treatments of centrifugation, washing, drying, removal of magnetic foreign matters and the like are carried out.
Comparative example 1:
the high-nickel ternary precursor in the example is prepared by adopting the following preparation method, and specifically comprises the following steps:
(1) Preparing sulfate solution A containing nickel ions, cobalt ions and manganese ions and having the total ion concentration of 120g/L, wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 96:1:3, industrial liquid alkali with the concentration of 8mol/L is used as precipitant solution B, and ammonia water with the concentration of 0.6mol/L is used as complexing agent solution C;
(2) 6000L of distilled water is added into a reaction kettle, 8mol/L of precipitator solution B and 0.6mol/L of complexing agent solution C are added, a base solution D with pH of 11.00 and ammonia concentration of 6g/L is obtained, the temperature of the base solution D is 35 ℃, and nitrogen is introduced into the base solution D for about 5 hours, so that the dissolved oxygen content of the base solution D is lower than 1mg/L. Adding the sulfate solution A, the precipitator solution B and the complexing agent solution C into the base solution D respectively according to the flow rates of 600L/h, 240L/h and 35L/h for coprecipitation reaction, wherein the ammonia concentration of a reaction system is 6g/L, the reaction pH is 9.60, the temperature is 35 ℃, the stirring rotation speed is 400rpm, after the coprecipitation reaction is started, nitrogen is continuously introduced for 5h, the nitrogen flow is 1000L/h, then air is introduced again for continuous reaction for about 60h, and the flow ratio of the air flow to the sulfate solution A is 0.8; stopping introducing the sulfate solution A, the precipitator solution B and the complexing agent solution C until the reaction is completed when the precursor particles grow to the target particle diameter of 3 mu m, ending the reaction to obtain a spherical high-nickel ternary precursor, and performing treatments such as centrifugation, washing, drying and removing magnetic foreign matters to obtain a spherical high-nickel ternary precursor finished product material.
Comparative example 2:
the high-nickel ternary precursor in the example is prepared by adopting the following preparation method, and specifically comprises the following steps:
(1) Preparing sulfate solution A containing nickel ions, cobalt ions and manganese ions and having the total ion concentration of 120g/L, wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 96:1:3, industrial liquid alkali with the concentration of 8mol/L is used as precipitant solution B, and ammonia water with the concentration of 0.6mol/L is used as complexing agent solution C;
(2) 6000L of distilled water is added into a reaction kettle, 8mol/L of precipitator solution B and 0.6mol/L of complexing agent solution C are added, a base solution D with pH of 11.00 and ammonia concentration of 1.5g/L is obtained, the temperature of the base solution D is 60 ℃, and nitrogen is introduced into the base solution D for about 5 hours, so that the dissolved oxygen content of the base solution D is lower than 1mg/L. Adding the sulfate solution A, the precipitator solution B and the complexing agent solution C into the base solution D respectively according to the flow rates of 600L/h, 240L/h and 8L/h for coprecipitation reaction, wherein the ammonia concentration of a reaction system in the coprecipitation reaction process is 1.5g/L, the reaction pH is 9.60, the temperature is 60 ℃, the stirring rotation speed is 400rpm, after the reaction is started, nitrogen is continuously introduced for 5h, the nitrogen flow is 1000L/h, then air is introduced for continuous reaction for about 60h, and the flow ratio of the air flow to the sulfate solution A is 0.8. And (3) stopping introducing the sulfate solution A, the precipitator solution B and the complexing agent solution C until the reaction is completed after the precursor particles grow to the target particle size of 3 mu m, ending the reaction to obtain a spherical high-nickel ternary precursor, and performing treatments such as centrifugation, washing, drying, removal of magnetic foreign matters and the like to obtain a spherical high-nickel ternary precursor finished product material.
Comparative example 3:
the high-nickel ternary precursor in the example is prepared by adopting the following preparation method, and specifically comprises the following steps:
(1) Preparing sulfate solution A containing nickel ions, cobalt ions and manganese ions and having the total ion concentration of 120g/L, wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 94:2:4, industrial liquid alkali with the concentration of 8mol/L is used as precipitant solution B, and ammonia water with the concentration of 0.6mol/L is used as complexing agent solution C;
(2) 6000L of distilled water is added into a reaction kettle, and then 8mol/L of precipitant solution B and 0.6mol/L of complexing agent solution C are added to obtain base solution D with pH of 11.5 and ammonia concentration of 12g/L, wherein the temperature of the base solution D is 50 ℃. Adding the sulfate solution A, the precipitator solution B and the complexing agent solution C into the base solution D according to the flow rates of 600L/h, 240L/h and 70L/h respectively to carry out coprecipitation reaction, wherein the ammonia concentration of a reaction system in the coprecipitation reaction process is 12g/L, the reaction pH is 11.4, the temperature is 50 ℃, and the stirring rotation speed is 400rpm; stopping introducing the sulfate solution A, the precipitator solution B and the complexing agent solution C until the reaction is completed when the precursor particles grow to the target particle diameter of 3 mu m, ending the reaction to obtain a spherical high-nickel ternary precursor, and performing treatments such as centrifugation, washing, drying and removing magnetic foreign matters to obtain a spherical high-nickel ternary precursor finished product material.
Performance test:
the primary particle length, primary particle diameter, specific surface area, tap density, D of the high nickel ternary precursors in examples 1 to 2 and comparative examples 1 to 3, respectively, were tested 50 And D max Data, wherein the specific surface area was tested using a Bei Shide H-2000PS2 type BET tester; the tap density is tested by adopting an Rake FT-100A tap density meter; d (D) 50 And D max The data are all tested by adopting a Markov laser particle sizer 3000; the specific test results are shown in table 1.
TABLE 1 Performance data for high Nickel ternary precursors in examples 1-2 and comparative examples 1-3
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Primary particle length nm | 200 | 320 | 700 | 300 | 640 |
| Primary particle diameter nm | 12 | 20 | 80 | 18 | 160 |
| Specific surface area m 2 /g | 64 | 45 | 15 | 50 | 16 |
| Tap density g/cm 3 | 1.68 | 1.72 | 1.76 | 1.21 | 1.31 |
| D 50 μm | 3.21 | 3.18 | 3.23 | 3.05 | 3.12 |
| D max μm | 6.37 | 6.24 | 6.44 | 11.35 | 9.79 |
As can be seen from table 1, the primary particle size of the high nickel ternary precursor in examples 1 and 2 is greatly reduced, and the specific surface area and tap density are both improved, compared with comparative example 3; close D 50 In the case of D of example 1 and example 2 max Significantly less than comparative example 3, indicating significantly better dispersibility and sphericity of the high nickel ternary precursors in examples 1 and 2; the primary particles of the high-nickel ternary precursor in comparative example 1 were larger in size, while the primary particles of the high-nickel ternary precursor in comparative example 2 were significantly finer, but were severely agglomerated, and were the same as D 50 Dmax is extremely large under the condition.
FIGS. 1 to 5 are SEM images of the high nickel ternary precursors of examples 1 to 2 and comparative examples 1 to 3, respectively, wherein FIGS. 1 (a) and 1 (b) are SEM images of the high nickel ternary precursors of example 1 with scales of 50 μm and 1 μm, respectively; FIGS. 2 (a) and 2 (b) are SEM images of the high nickel ternary precursor of example 2 with a scale of 50 μm and 1 μm, respectively; FIGS. 3 (a) and 3 (b) are SEM images of the high nickel ternary precursor of comparative example 1 with scales of 50 μm and 1 μm, respectively; FIGS. 4 (a) and 4 (b) are SEM images of the high nickel ternary precursor of comparative example 2 with a scale of 50 μm and 1 μm, respectively; FIGS. 5 (a) and 5 (b) are SEM images of the high nickel ternary precursor of comparative example 3 with scales of 50 μm and 1 μm, respectively; as can be seen from comparison of fig. 1 to 5, the primary particle size of the high nickel ternary precursor prepared in comparative example 3 is large, and the diameter is thick, so that the specific surface area is small; the primary particle size of the high-nickel ternary precursor prepared by adjusting the condition of the base solution, the reaction temperature, the ammonia concentration and the like in the embodiment 1 and the embodiment 2 of the invention is small, the specific surface area and the tap density are both improved, and particularly the specific surface area is greatly improved; in contrast, in the comparative example 1, although the reaction condition is adopted at low temperature, the primary particle refinement of the prepared high-nickel ternary precursor is not obvious due to the higher ammonia concentration; in comparative example 2, although the primary particles of the prepared high-nickel ternary precursor are obviously refined due to the extremely low ammonia concentration and the high reaction temperature, obvious secondary nucleation exists, the sphericity is extremely poor, and the agglomeration is extremely serious.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (2)
1. A preparation method of a high-nickel ternary precursor is characterized by comprising the following steps of: the method comprises the following steps:
adding metal salt, ammonia water and a precipitator into a base solution containing the precipitator and the ammonia water and having the oxygen content lower than 1mg/L respectively for coprecipitation reaction to obtain the high nickel ternary precursor;
the coprecipitation reaction is as follows: firstly, introducing protective gas to react, then introducing oxygen-containing gas to react,
the temperature of the coprecipitation reaction is 25-40 ℃, the pH of the coprecipitation reaction is 9.5-10, and the concentration of ammonia water is 0.5-1.5 g/L;
the concentration of ammonia water in the base solution is 0.5-1.5 g/L, the pH value is 10.5-11.0, and the temperature is 25-40 ℃;
the specific surface area of the high-nickel ternary precursor is 45-70m 2 /g；
The flow ratio of the shielding gas to the metal salt solution is (2-3): 1, a step of;
the flow ratio of the oxygen-containing gas to the metal salt solution is (0.1-0.5): 1, a step of;
in the coprecipitation reaction, the time required for introducing protective gas is 4-6 hours; the time required for introducing the oxygen-containing gas is 54-66 hours.
2. The method for preparing the high-nickel ternary precursor according to claim 1, wherein the method comprises the following steps: the metal salt is a metal salt solution, the adding flow rate of the metal salt solution is 100-800L/h, and the total concentration of metal ions in the metal salt solution is 115-125 g/L; the adding flow of the precipitant is 50-400L/h; the adding flow of the ammonia water is 1-100L/h; the time required for the step of adding the metal salt, the ammonia water and the precipitant is 60-70 h.
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